CN113754613B - Method for benzene thio cyclic ether of 4-enol - Google Patents
Method for benzene thio cyclic ether of 4-enol Download PDFInfo
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- CN113754613B CN113754613B CN202111134252.XA CN202111134252A CN113754613B CN 113754613 B CN113754613 B CN 113754613B CN 202111134252 A CN202111134252 A CN 202111134252A CN 113754613 B CN113754613 B CN 113754613B
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- 238000000034 method Methods 0.000 title claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title description 5
- -1 benzene thio cyclic ether Chemical class 0.000 title description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 14
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000006266 etherification reaction Methods 0.000 claims description 10
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 8
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004122 cyclic group Chemical class 0.000 abstract description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- VUNFOJWKJSYIDH-SREVYHEPSA-N Cis-4-Decenol Chemical compound CCCCC\C=C/CCCO VUNFOJWKJSYIDH-SREVYHEPSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000001160 (2R,3R)-2-methyloxolane-3-thiol Substances 0.000 description 1
- 239000001356 (3R)-3-sulfanylbutan-2-one Substances 0.000 description 1
- 239000001082 (3R)-3-sulfanylpentan-2-one Substances 0.000 description 1
- BVARCEWAKNFRCH-UHFFFAOYSA-N 2-(phenylsulfanylmethyl)oxolane Chemical compound C1CCOC1CSC1=CC=CC=C1 BVARCEWAKNFRCH-UHFFFAOYSA-N 0.000 description 1
- ZFFTZDQKIXPDAF-UHFFFAOYSA-N 2-Furanmethanethiol Chemical compound SCC1=CC=CO1 ZFFTZDQKIXPDAF-UHFFFAOYSA-N 0.000 description 1
- RUYNUXHHUVUINQ-UHFFFAOYSA-N 2-Methyl-3-furanthiol Chemical compound CC=1OC=CC=1S RUYNUXHHUVUINQ-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- XLMPYCGSRHSSSX-UHFFFAOYSA-N 3-Mercapto-2-butanone Chemical compound CC(S)C(C)=O XLMPYCGSRHSSSX-UHFFFAOYSA-N 0.000 description 1
- SZECUQRKLXRGSJ-UHFFFAOYSA-N 3-Mercapto-2-pentanone Chemical compound CCC(S)C(C)=O SZECUQRKLXRGSJ-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- DBPHPBLAKVZXOY-UHFFFAOYSA-N Tetrahydro-2-methyl-3-furanthiol Chemical compound CC1OCCC1S DBPHPBLAKVZXOY-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- SMIALSADYPNJJR-UHFFFAOYSA-N oxo-phenoxy-phenyl-sulfanylidene-$l^{6}-sulfane Chemical compound C=1C=CC=CC=1S(=S)(=O)OC1=CC=CC=C1 SMIALSADYPNJJR-UHFFFAOYSA-N 0.000 description 1
- JWUKZUIGOJBEPC-UHFFFAOYSA-N phenyl thiohypochlorite Chemical compound ClSC1=CC=CC=C1 JWUKZUIGOJBEPC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003448 sulfenic acid esters Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本发明涉及一种4-烯醇的苯硫基环醚化方法。The invention relates to a method for phenylthio ring etherification of 4-enol.
鉴于含硫香料独特的香气特性，研究开发新型的多官能团含硫香料分子成为近些年的研究热点之一。大量的研究表明，含1，2-氧硫结构单元的化合物普遍具有肉香、焦香味，如重要的肉香味化合物2-甲基-3-呋喃硫醇、2-甲基-3-四氢呋喃硫醇、3-巯基-2-丁酮、3-巯基-2-戊酮，重要的烤香类化合物糠硫醇等。同时，1，2-氧硫官能团除了在多官能团香料中广泛存在外，还是很多生物活性化合物的结构单元和有机合成中非常有用的合成子，因此研究开发1，2-氧硫官能团化合物的新方法具有重要的意义。In view of the unique aroma characteristics of sulfur-containing spices, the research and development of new multifunctional sulfur-containing spice molecules has become one of the research hotspots in recent years. A large number of studies have shown that compounds containing 1,2-oxosulfur structural units generally have meaty and burnt aromas, such as important meaty compounds 2-methyl-3-furanthiol, 2-methyl-3-tetrahydrofuranthiol Alcohol, 3-mercapto-2-butanone, 3-mercapto-2-pentanone, important roasted aroma compound furfuryl mercaptan, etc. At the same time, 1,2-oxosulfur functional group is not only widely present in multifunctional spices, but also a very useful synthon in many bioactive compounds and organic synthesis. method is of great importance.
在众多的1，2-氧硫官能团化合物合成方法中，烯烃与亲电的含硫试剂作用经过氧硫基化反应是最为直接的方法。文献报道的亲电的含硫试剂主要包括次磺酰氯、二硫醚、四氟硼酸二甲基甲硫基硫鎓盐、N-烃硫基酰亚胺、次磺酸酯、磺酰肼和二甲亚砜。其中苯硫基化试剂主要有二苯基二硫醚、苯硫基氯和硫代苯磺酸苯酯。本发明方法中，开发了一种以甲基苯基亚砜和草酰氯组合试剂作为苯硫基化试剂的新的苯硫基化方法。以不饱和醇为原料，通过“一锅法”制备含有1，2-氧硫官能团的苯硫基环醚产物。Among the many synthetic methods of 1,2-oxysulfur functional group compounds, the most direct method is the reaction of olefins with electrophilic sulfur-containing reagents through oxythiolation. The electrophilic sulfur-containing reagents reported in the literature mainly include sulfenyl chloride, disulfide, dimethylsulfenyl tetrafluoroborate, N-hydrocarbyl thioimide, sulfenic acid ester, sulfonyl hydrazide and Dimethyl sulfoxide. Among them, the phenylthiolation reagents mainly include diphenyl disulfide, phenylthio chloride and phenyl thiobenzenesulfonate. In the method of the present invention, a new thiophenylation method using a combined reagent of methyl phenyl sulfoxide and oxalyl chloride as a thiophenylation reagent is developed. Using unsaturated alcohols as raw materials, thiophenylcyclic ether products containing 1,2-oxosulfur functional groups were prepared by "one-pot method".
本发明的目的是提供一种新的4-烯醇的苯硫基环醚化方法。其特征是以甲基苯基亚砜和草酰氯为起始原料，然后在(±)-樟脑磺酸的催化下与4-烯醇反应，得到含有1，2-氧硫结构单元的苯硫基环醚化产物。本发明的制备方法具有原料易得、操作简便的优点。反应式如下：The purpose of this invention is to provide a kind of phenylthio ring etherification method of new 4-enol. It is characterized by using methyl phenyl sulfoxide and oxalyl chloride as starting materials, and then reacting with 4-enol under the catalysis of (±)-camphorsulfonic acid to obtain phenylsulfide containing 1,2-oxosulfur structural unit Cyclic etherification products. The preparation method of the invention has the advantages of readily available raw materials and simple operation. The reaction formula is as follows:
本发明涉及结构式如下所示的不饱和醇的苯硫基环醚化产物：The present invention relates to the phenylthio ring etherification product of the unsaturated alcohol shown in structural formula as follows:
其主要过程是：在0℃条件下，将草酰氯的乙腈溶液滴加到甲基苯基亚砜的乙腈溶液中，搅拌10min后，转移至油浴锅，加热到100℃时，将4-烯醇和(±)-樟脑磺酸加入，回流8小时，得到具有1，2-氧硫结构单元的苯硫基环醚化产物，产率60％以上。The main process is: at 0°C, drop the acetonitrile solution of oxalyl chloride into the acetonitrile solution of methyl phenyl sulfoxide, stir for 10 minutes, transfer to an oil bath, and when heated to 100°C, add 4- Add enol and (±)-camphorsulfonic acid, and reflux for 8 hours to obtain a phenylthio ring etherification product with a 1,2-oxosulfur structural unit, with a yield of more than 60%.
本发明方法中制备的苯硫基环醚化产物结构通过核磁共振进行了确认。分析结果附在实施例后。The structure of the thiophenyl ring etherification product prepared in the method of the present invention is confirmed by nuclear magnetic resonance. Analysis result is appended after embodiment.
具体实施方式Detailed ways
(1)2-((苯硫基)甲基)四氢呋喃的制备(1) Preparation of 2-((phenylthio)methyl)tetrahydrofuran
向三口烧瓶中加入10mL无水乙腈和甲基苯基亚砜(15mmol，1.8mL)，待体系温度降至0℃以下，通过25mL的恒压滴液漏斗缓慢加入草酰氯(3.75mmol，0.33mL)的无水乙腈(10mL)溶液，滴加完毕后，在0℃下搅拌10min。然后移至油浴锅，加热至100℃时，依次加入4-戊烯-1-醇(5mmol，0.43g)和0.12g(±)-樟脑磺酸(0.5mmol)，继续回流8h。TLC跟踪，烯醇反应完毕后，旋蒸除去乙腈，加入二氯甲烷，转移至分液漏斗中，分别用饱和碳酸氢钠溶液和饱和氯化钠溶液洗涤两次，无水硫酸钠干燥，过滤，旋蒸。得到的粗产物经过柱层析分离(200-300目硅胶；石油醚∶乙酸乙酯＝60∶1)，得到4-戊烯-1-醇的苯硫基环醚化产物2-((苯硫基)甲基)四氢呋喃0.62g，产率为64％。1H NMR(300MHz，CDCl3)：δ＝7.37(dd，J＝7.2，1.2Hz，2H，H-o-phenyl)，7.26(td，J＝7.2，1.2Hz，2H，H-m-phenyl)，7.16(tt，J＝7.2，1.2Hz，1H，H-p-phenyl)，4.05(quin.，J＝6.0Hz，1H，H-C2)，3.90(dt，J＝9.0，6.0Hz，1H，H-C5，A part ofABX)，3.75(td，J＝9.0，6.0Hz，1H，H′-C5，B part ofABX)，3.15(dd，J＝13.0，5.8Hz，1H，H-CH2SPh)，2.97(dd，J＝13.0，6.8Hz，1H，H′-CH2SPh)，2.14-1.98(m，1H，H-C3)，1.96-1.78(m，2H，H-C4)，1.71-1.62(m，1H，H′-C3)。13C NMR(75MHz，CDCl3)：δ＝136.3，129.1，128.8，125.9，77.5，68.2，38.8，30.8，25.7。Add 10mL of anhydrous acetonitrile and methyl phenyl sulfoxide (15mmol, 1.8mL) into the three-neck flask, wait until the temperature of the system drops below 0°C, slowly add oxalyl chloride (3.75mmol, 0.33mL) through a 25mL constant pressure dropping funnel ) in anhydrous acetonitrile (10 mL), after the dropwise addition was completed, stir at 0° C. for 10 min. Then move to an oil bath, and when heated to 100°C, add 4-penten-1-ol (5mmol, 0.43g) and 0.12g (±)-camphorsulfonic acid (0.5mmol) successively, and continue to reflux for 8h. TLC tracking, after the enol reaction is complete, acetonitrile is removed by rotary evaporation, dichloromethane is added, transferred to a separatory funnel, washed twice with saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered ,Rotary evaporation. The obtained crude product was separated by column chromatography (200-300 mesh silica gel; petroleum ether: ethyl acetate = 60: 1), to obtain the phenylthio ring etherification product 2-((benzene) of 4-penten-1-ol Thio)methyl)tetrahydrofuran 0.62g, yield 64%. 1 H NMR (300MHz, CDCl 3 ): δ=7.37 (dd, J=7.2, 1.2Hz, 2H, Ho-phenyl), 7.26 (td, J=7.2, 1.2Hz, 2H, Hm-phenyl), 7.16( tt, J=7.2, 1.2Hz, 1H, Hp-phenyl), 4.05 (quin., J=6.0Hz, 1H, H-C2), 3.90 (dt, J=9.0, 6.0Hz, 1H, H-C5, A part of ABX), 3.75 (td, J=9.0, 6.0 Hz, 1H, H'-C5, B part of ABX), 3.15 (dd, J=13.0, 5.8 Hz, 1H, H-CH 2 SPh), 2.97 ( dd, J=13.0, 6.8Hz, 1H, H'-CH 2 SPh), 2.14-1.98(m, 1H, H-C3), 1.96-1.78(m, 2H, H-C4), 1.71-1.62(m , 1H, H'-C3). 13 C NMR (75 MHz, CDCl 3 ): δ = 136.3, 129.1, 128.8, 125.9, 77.5, 68.2, 38.8, 30.8, 25.7.
(2)顺式-2-戊基-3-(苯硫基)四氢-2H-吡喃的制备(2) Preparation of cis-2-pentyl-3-(phenylthio)tetrahydro-2H-pyran
向三口烧瓶中加入10mL无水乙腈和甲基苯基亚砜(15mmol，1.8mL)，待体系温度降至0℃以下，通过25mL的恒压滴液漏斗缓慢加入草酰氯(3.75mmol，0.33mL)的无水乙腈(10mL)溶液，滴加完毕后，在0℃下搅拌10min。然后移至油浴锅，加热至100℃时，依次加入顺式-4-癸烯-1-醇(5mmol，0.87g)和0.12g(±)-樟脑磺酸(0.5mmol)，继续回流8h。TLC跟踪，烯醇反应完毕后，旋蒸除去乙腈，加入二氯甲烷，转移至分液漏斗中，分别用饱和碳酸氢钠溶液和饱和氯化钠溶液洗涤两次，无水硫酸钠干燥，过滤，旋蒸。得到的粗产物经过柱层析分离(200-300目硅胶；石油醚∶乙酸乙酯＝250∶1)，得到顺式-4-癸烯-1-醇的苯硫基环醚化产物顺式-2-戊基-3-(苯硫基)四氢-2H-吡喃0.83g，产率为63％。1H NMR(300MHz，CDCl3)：δ＝7.41(dd，J＝7.2，1.5Hz，2H，H-o-phenyl)，7.26(td，J＝7.2，1.5Hz，2H，H-m-phenyl)，7.18(tt，J＝7.2，1.5Hz，1H，H-p-phenyl)，4.06-4.00(m，1H，H-C2)，3.94-3.88(m，1H，H-C6，A part ofABX)，3.81-3.70(m，1H，H′-C6，B part ofABX)，3.18(dt，J＝8.6，4.4Hz，1H，H-C3)，2.05-1.20(m，12H，H-C4，H-C5，H-C1-pentyl，H-C2-pentyl，H-C3-pentyland H-C4-pentyl)，0.87(t，J＝6.7Hz，3H，CH3)。13C NMR(75MHz，CDCl3)：δ＝136.1，131.1，128.7，126.3，80.7，68.7，53.2，31.7，31.1，28.3，26.9，26.2，22.5，14.0。Add 10mL of anhydrous acetonitrile and methyl phenyl sulfoxide (15mmol, 1.8mL) into the three-neck flask, wait until the temperature of the system drops below 0°C, slowly add oxalyl chloride (3.75mmol, 0.33mL) through a 25mL constant pressure dropping funnel ) in anhydrous acetonitrile (10 mL), after the dropwise addition was completed, stir at 0° C. for 10 min. Then move to an oil bath, and when heated to 100°C, add cis-4-decen-1-ol (5mmol, 0.87g) and 0.12g (±)-camphorsulfonic acid (0.5mmol) successively, and continue to reflux for 8h . TLC tracking, after the enol reaction is complete, acetonitrile is removed by rotary evaporation, dichloromethane is added, transferred to a separatory funnel, washed twice with saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered ,Rotary evaporation. The obtained crude product was separated by column chromatography (200-300 mesh silica gel; petroleum ether: ethyl acetate = 250:1), and the phenylthio ring etherification product of cis-4-decen-1-ol, cis - 0.83 g of 2-pentyl-3-(phenylthio)tetrahydro-2H-pyran, the yield was 63%. 1 H NMR (300MHz, CDCl 3 ): δ=7.41 (dd, J=7.2, 1.5Hz, 2H, Ho-phenyl), 7.26 (td, J=7.2, 1.5Hz, 2H, Hm-phenyl), 7.18( tt, J=7.2, 1.5Hz, 1H, Hp-phenyl), 4.06-4.00 (m, 1H, H-C2), 3.94-3.88 (m, 1H, H-C6, A part of ABX), 3.81-3.70 ( m, 1H, H'-C6, B part of ABX), 3.18 (dt, J=8.6, 4.4Hz, 1H, H-C3), 2.05-1.20 (m, 12H, H-C4, H-C5, H- C1-pentyl, H-C2-pentyl, H-C3-pentyl and H-C4-pentyl), 0.87 (t, J=6.7Hz, 3H, CH3 ). 13 C NMR (75 MHz, CDCl 3 ): δ=136.1, 131.1, 128.7, 126.3, 80.7, 68.7, 53.2, 31.7, 31.1, 28.3, 26.9, 26.2, 22.5, 14.0.
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